Abstract

Trimethylsilylacetylene undergoes clean cis-addition to alkynyl sulfones or esters 1 in the presence of catalytic palladium acetate and tri(2,6-dimethoxyphenyl)phosphine to give (E)-1-sulfonyl (or ethoxycarbonyl)-4-trimethylsilyl-substituted 1,3-enyne 2 in excellent yields. The cross-coupling reaction of (E)-1-sulfonyl (or ethoxycarbonyl)-4-trimethylsilyl-substituted 1,3-enyne 2 with (E)-alkenyl iodides 3 in the presence of Pd(PPh3)4 and tris(diethylamino)sulfonium trimethyldifluorosilicate (TASF) affords stereoselectively (1E,5E)-1-sulfonyl (or ethoxycarbonyl)-substituted 1,5-dien-3-ynes 4 in good yields.

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